Terpene halo-alkyl-ether-amine condensation product



Patented Apr. 13, 1943 TERPENE HALO-ALKYL-ETHER-AMINE CONDENSATION raonuc'r Lyle W. Rotlienberger, Brunswick, 61., assignor to Hercules Powder Company, Wilmington, Del,,.a crp0rati0n of Delaware No Drawing. Application August 21, 1940, Serial No. 353,529

Claims. (c1. ago-570.5)

This invention relates to a'terpene'ether-amine condensation product and, more particularly, to a condensation product prepared by condensing an ether of a terpene radical and a halogen substituted organic radical withan amine.

It is an object of the present invention to effect the condensation of an ether ofa terpene radical and a halogen substituted organic radical with an amine.

Another object is to, effect the condensatlonoi a Preferably, the reactants are" employed in such proportion that from about 1 to about 4 mols of V v the amine are present for each mol of the ether terpinyl ether of a halogen substituted aliphatic radical with an amine.

Another object is to effect the condensation of a terpinyl haloalkyl ether with a primary secondary, or tertiary alkyl, aryl oraralkyl amine.

Another object is to eflfect the condensationoi a terpinyl haloalkyl etherwith an alkylol amine.

to be condensed. Where the amine is a polyamine or wherea polyhalog en substituted terpene ether containing a plurality of halogengroups on a single organic radical or a plurality of halogen, substituted'etherifled organic groups, is used, the molar proportions are adjusted accordingly so thatthere is presented by the amine from about 1 to about 4 amine groups per halogen group in an etherified organic radical of said ether.

Usually the mixture is agitated during the reaction either by the provision of a suitable agitator or as a result or the heating or refluxing oi the mixture. If desired, the reaction may be car-- ried out under elevated pressure in a suitable Another object is to eflect thecondensatlon of a terpene haloalkyl ether with a tertiary amine.

Another object is to make available the hydrohalideaddition products" of the foregoing con-' densation products.

Another object isto make available the alkyl halide addition products of the foregoing con 1 densation products;

' Still another object is to devise a process for the production of the foregoing compounds.

In accordance with the present invention, condensation is effected between a terpene halo-substituted ether and an amine. of procedure comprises heating to an elevated temperature a mixture of an ether of a terpene radical and a halogen substituted organic radical with an amine The reaction is usually carried out in the presence of a catalyst which may conveniently be an amine hydrohalide addition product in an amount ranging from about 0.2 to about 0.5 mol per mol of ethertaken. Examples 'of catalysts other than amine hydrohalide addition productswhich maybe used are hydroiodic acid, hydrobromic acid, hydrochloric acid, sulfuric acid, acetic acid, p-toluene sulfonic acid, ferrous iodide, etc. Following the reaction, the mixture is allowed to 'cool and is then treated with an alkali so as to decompose hydrohalide-ramine catalyst and hydrohalide-condensate addition products, and treated to recover the condensation product, the product thus obtained comprising the condensate.

A typical method.

autoclave. I

The use of equimolar proportions .of the ether and the amine will yield the desired condensation productwith somewhat less side reactions.

However, the use-of an excess of the amine is frequently desirable in order to eflect better yields on-the' basis of theether' take I Although use of a catalyst increases somewhat the amount of by-products produced, such use of a catalyst is generally desirable becauseqof the more"rapid condensation effected therewith.

' condensed with the terpene' halo-substituted ether, and may be present either in the form of separately prepared hydrohalide addition prod not or as'a result of the incorporation in the reactive mixture of a hydrohalide such as hydro.-

chlorio', hydrobromic, or hydroiodic acid which:

reacts with theaniine.

The reaction temperaturemay vary between about 0. and about 250? 0., but a preferred preferable time range is between about 4 and about 1 0 hours,

As the ether employed in carrying out thecondensation of the present invention, I may use terpinyl betachloroethyl ether prepared in the,

manner described in thecopending application of D, H. Sheflleld, Serial No. 301,761, filed October 28, 1939. A method described in that application for the production of this ether is as follows:

Four hundred g. of alpha pin'ene were added to 600 g. of ethylene chlorohydrin and 12 g. of 75% by weight sulfuric acid and the mixture well agitated. The reaction which took place evolved heat, the temperature being maintained at 45 C. by cooling. After 3 hours, the reaction was complete. Acid and excess ethylene chlorohydrin were then removed by two washes of about 500 g. each of 10% by weight aqueous sodium carbonate solution. The resulting oil was then fractionated into two components by distillation. The fraction coming over between 115 and 130 C. at 8 millimeters absolute pressure consisted essentially of terpinyl beta-chloroethyl ether. This compound may be characterized by the following formula:

in accordance with the present invention, the principal condensation product may be designated as terpinyl beta-monoethyl aniline ether a (i. e. the mono-anilide of the ethyl ether of alpha terpineol) and may be characterized by the fol lowing formula:

Other terpene ethers which are suitable are,

naphthylamine, beta naphthylamine, etc.; secondary aromatic amines, such as methyl aniline, diphenyl amine, etc.; tertiary aromatic amines, such as methyl ethyl aniline, dimethyl aniline, triphenyl amine, etc.; aralkyl amines, such as benzy] amine; aliphatic amines, such as methyl, ethyl, propyl, butyl, and octyl amine, dimethyl,

'diethyl, dipropyl, dibutyl, and dioctyl amine,

trimethyl amine, triethyl amine, etc.; diamines such as ethylene diamine, phenylene diamine, etc.; mixed aliphatic amines, such as methyl ethyl amine, ethyl butyl amine, ethylbutyl octyl amine, etc. The amine employedmay, if desired,-

be an alkylolamine, such. as monoethanolamine, diethanolamine, or a tertiary alkylolamlne such as triethanolamine. Where a polyamine is employed, one mol thereof is equivalent to a' number of mols of a monoamine equal to the number of amino groups present in the polyamine. Thus where a diamine is employed, only one-half of the usual molar quantity need be used.

, Where a tertiary amine is employed as the reactant, the condensation product comprises a for example, terpinyl chloropropyl ether, terpinyl.

J chlorobutyl ether, terpinyl chloroamyl ether,

terpinyl chloro-octyl ether, terpinyl chlorophenyl ether, the terpinyl ether 01'. glycerin monochlorohydrin, terpinyl chloro-o ctadecamethylene ether, etc., the corresponding fenchyl, bornyl, isobomyl, etc. ethers, and' the corresponding bromo and iodo substituted ethers. The terpene radical may be either a hydrocarbon radical or an oxygenated hydrocarbon radical such as a terpene radical, containing one or more hydroxy groups, keto groups, carboxyl groups, etc. The organic group may contain one or more halogen groups. prepared by reacting alpha pinenewith glycerin dlchlorohydrin may be employed. I

The condensation proceeds most readily when using an iodine substituted ether, less readily when using 'a bromine substituted ether and still 00 Thus, terpinyl dichloropropyl ether,-

less readily when using a chlorine substituted quaternary ammonium compound; for example, when terpinyl beta-chloroethyl ether is reacted with trimethyl amine, the condensate appears to have the following configuration:

where T is the terpinyl radica1 (having the empirical formula Cm'tln, the structural formula depending upon whether derived from alpha, beta or gamma terpinene, alpha or beta phellandrene, terpinolene, pseudo limonene, dipentene, Or other pmethadiene, and upon which of the two double bonds of. the methadiene has been eliminated during the formation of the ether). Thespeed of reaction and the yield of the quaternary ammonium compounds depend, upon the chemical configuration of the reactants, upon the solvent employed for the reactants upon the particular ha1ogen with which the terpene ether is substituted and upon numerous other factors. The quaternary ammonium compound resulting from the reaction of terpinyl beta-chloroethyl ether with methyl ethyl aniline is especially useful.

The quaternary ammonium compounds may also be prepared byreacting the condensate of a terpene halo-ethyl ether and a secondary amine with an alkyl halide. One example of such a compound is that resulting from the reaction of methyl chloride with the condensate from terpinyl beta-chloroethyl ether and dimethyl aniline.

If desired, the secondary or tertiary condensation products of the present invention, after washing with aqueous sodium hydroxide or the 4 in the same manner as that described above.

aromatic amines, such as aniline, toluidine, alpha (5 Where quaternary salts are formed, they may,

:if water soluble, be removed by extraction of the reaction mixture with water. The aqueous solution containing the quaternary salt may then be concentrated by evaporation. The quaternary salt when water soluble may be stored or sold in concentrated aqueous solution.

where T is a terpene radical such as terpinyl. where R is an alkylene group, and where R1 and R2 are either hydrogen organ organic radical such as an aliphatic group, an aromatic group, an aralkyl group, an alkaryl group, or a hydroxyl substituted group of this type, etc. Preferably, at least one of R1 and R2 is a hydrocarbon or a hydroxyl substituted hydrocarbon nucleus of the type Just described. The'nitrogen atom is trivalent in the case of the condensates from primary and secondary amines and is pentavalent in the case of the condensates from the tertiary amines or of the hydrohalide salts of the condensates from primary or secondary amines.

The hydrohalide addition products formed by the addition of a hydrohalide such as hydrochloric acid to the condensate from a primary and secondary amine, are formed during the reaction as an intermediate, from which the condensate with trivalent nitrogen may be obtained by the neutralization with a base and may be characterized by the general formula:

The'quaternary ammonium compounds may i be characterized by the general formula:

where T is a terpene radical as before, R is an alkylene group, R3, R4, and R5 are hydrocarbon radicals of hydroxyl substituted hydrocarbon radicals and where X is a negative group, such as, a halogen group, a hydroxyl group or the like.

The quaternar ammonium hydroxides (where X in the foregoing formula is a hydroxyl group) may be prepared in any suitable manner for extains unsatu'rated double bonds, under some circumstances reaction with the amine takes place additionally at such double bonds. Theamount of condensation of .the amine at unsaturated centers oi the terpene other may be greatly reduced by the use of molar proportions of the reactants, or by carrying out the reaction in the absence of a catalyst. The product of such con- I 3 'densation' may be characterized by the general 7 formula: V V lii\ n, xr o-ie-x 2 I RI where T, R, R1, and R2 have the same significance as above. For example, where terpinyl betachloroethyl ether is reacted with aniline under conditions which give rise to such condensation, the product is believed to be characterized by "the following formula:

The process and the product of such condensation are deemed to vbe'within the scope of the reaction of the terpene halo-alkyl 'ether with a primary or secondary amine, the condensation product which is present in the form of the hydrohalide addition product may be neutralized with alkali. The alkali is usually employed in the form of an aqueous solution of concentration varying from about 5 to about 50% by weight. Suitable alkalies are sodium and potassium hydroxides, sodium and potassium carbonates, calcium hydroxide, ammonium hydroxide, etc. At least one mol of alkali must be used per mol of terpene halo-alkyl ether employed in order to give complete neutralization. Following treatment with alkali, the product may be washed with water, dried, and purified in any suitable manner as by distillation to remove unreacted amine therefrom and to recover a pure product.

If desired, the reaction may be carried out in stages, by neutralizing the reaction product after each stage with an alkali to convert the hydrohalide addition product of the condensation product to the condensate itself, washing with water, drying, adding terpene halo-alkyl ether and additional catalyst to the condensate, and reacting to yield the condensate of the next degree of condensation'; For example, this may be carried out by reacting one mol of terpinyl beta-chloroethyl ether with one mol of aniline inflthe presence off 0.3 mol of aniline hydrochloride, treating the reaction mixture with 1.3 mols of sodium hydroxide in the form ofan aqueous solution, separatin the aqueous layer, washing the oily condensate, distilling the resulting condensate to uemove aniline therefrom, adding one mol of ierpinyl beta-chloroethyl ether and some additicnal catalyst. and reacting the mixture by heating to yield a tertiary condensation product. If desired, this procedure may be repeated on the of aniline hydrochloride.

Example 1 One hundred and sixty-eight grams of aniline were treated with dry hydrogen chloride until the weight increased 7.2 g. The mixture comprised 1.6 mols of aniline and 0.2 mol of aniline hydro: chloride. There was added to the mixture 100 g. of terpinyl beta-chloroethyl ether (0.46 mol) and the mixture was refluxed for 8 hours by heating in an oil bath at 200210 C. The mixture was allowed to cool and was then agitated with 175 c. c. of 25% sodium hydroxide solution. The oily layer was separated, washed with sodium chloride solution and dried over solid sodium hydroxide. The mixture was iractior'ially distilled at reduced pressure of from 5 to 1.5 millimeters absolute. The fraction coming over. at 5 mm. and between 45 and 100 C. was unreacted aniline, The fraction coming over at between 130 and 192 C. at a pressure of 3-1.5 mm. comprised the condensate in accordance with the present invention.

. Example 2 Eight hundred forty grams of aniline were treated with dry hydrogen chloride until the weight increased 36 g. whereupon some crystalline aniline hydrochloride separated out. The mixture comprised 8 mols oi aniline and 1 mol There was added to the mixture 500 g. (2.31 mols) of terpinyl beta- Vapor Fraction te m a i g Color 1.8 157 Light amber. l-l. 4 109 D0. 0.8-1.0 185 D0.

1.1 259 Dark brown.

Analysis indicated that fractions 1 to 3 comprise a product wherein condensation has taken place only at the halogen center, and that fraction 4 is a product wherein condensation has taken place both at the halogen center and at the terpinyl double bond.

Example 3 A mixture oi 108 g. (0.5 mol) of terpinyl betachloroethyl ether, 186 g. aniline (2 mols) and 12.9 g. aniline hydrochloride (0.1 mol) was refluxed for 8 hours at 190-195 C. The reaction mixture was neutralized by treatment with 150 and the oil layer dried over solid sodium hydroxide.

Excess aniline was removed by distilling the oily layer at 7 mm. pressure, the aniline passing over at 60 C. When the vapor temperature started rising rapidly to C., distillation was stopped. The residue which constituted'the condensate consisted oi g. of a dark colored viscous liquid. The material appeared to contain some product which forms by condensation of aniline at the double bond of the terpinyl beta-chloroethyl ether.

Example 4 A mixture or 50 g. terpinyl beta-chloroethyl ether "(0.23 mol) and 15 g. monoethanolamine (0.24 mol) was refluxed for 5 hours at 190-200 C. After washing with 2% sodium hydroxide, extraction with ether and evaporation of the solvent, there was obtained a dark green liquid comprising the condensate oi the present inven-- tion.

Example 5 A mixture of 72 g. terpinyl beta-chloroethyl ether (0.33 mol) and 50 g. of. triethanolamine (0.35 mol) was heated at 180-200 C. for 4 hours. The reaction mixture consisted of dark green liquid and. a quantity of white water insoluble solid which was filtered off. The liquid was washed with water and dried. This liquid contained quaternary amine condensate.

Example 6 A mixture of 50 g. 01 terpinyl beta-chloroethyl ether (0.2311101), c. c. of a 30% aqueous solution of trimethyl amine (0.76 mol) and about A mixture of 50 g. of terpinyl chloroethyi ether (0.2311101), 12 g.'of ethylene diamine (0.21 mol) and 0.1 g. ii'errous iodide was heated at -165 C. for 8 hours. was a viscous red liquidcontaining considerable solid. The mixture was extracted with 200 c. c. of ether and the insoluble solid filtered off. The ether solution was washed with 150 c. c. of 12% sodium hydroxide and the solvent evaporated, yielding the condensate.

The reaction products made in accordance with the present invention are useful in a number of arts. The products made by condensation of the terpene halo-alkyl ether with a primary or a secondary amine are exceedingly useful as anti-oxidants for wood rosin. Thus, wood rosin containing 1%oi' the condensatio' product of terpinyl beta-chloroethyl ether with aniline made in accordance with Examples 1 to 3 shows a marked reduction in weight increase upon ex- ,posure to oxygen under pressure, this increase in weight being less than /n that for pure wood rosin and less that of wood rosin containing 1% phenyl beta-naphthylamine. The .condensation products made from the primary and secondary amines are also very useful as anti- The reaction product Suite A, and parts of normal butyl alcohol 5 Zinc oxide 25 Stearic acid 5 Captax (mercaptobenzothiazole) Terpinyl beta-chloroethyl etheraniiine condensate made in accordance with Example 1 and distilling over at 150-l60 C. at 1.5 mm. pressure 5 Sulfur 15 These ingredients were milled together and test pieces made therefrom were aged 7 days at 80 C. in circulating air. These test pieces retained 74% of their initial tensile strength while a comparison specimen containing no anti-oxidant and aged under the same conditions retained only 63% of its tensile strength.

The compounds of the present invention are also useful as plasticizers for resins, plastics, cellulose derivatives, etc., as anti-oxidants for dry paper sizes made from rosin, as flotation agents for non-metallic minerals, and as stabilizers for nitroglycerine explosives. The quaternary ammonium compounds made in accordance with the present invention are valuable in textile treating.

In this specification and in the claims appended thereto, the term hydrohalide is intended to denote hydrogen chloride, hydrogen bromide and hydrogen iodide, and the term halogen to designate chlorine, bromine and iodine.

It is to be understood that the details and examples hereinbefore set forth are illustrative only and that the invention as broadly described and claimed is in no way limited thereby.

What I claim and desire to protect by Letters Patent is:

l. The process which comprises heating for a period ranging from about 4 to about 10 hours at a temperature of from about 170 C. to about 210 C. a mixture of terpinyl beta-chloroethyl ether and aniline in the ratio of from about 1 to about 4 mols of aniline-per mol of said ether in the presence of from about 0.2 to about 0.5 mol of aniline hydrochloride per mol of said ether, cooling, commingling the mixture with an aqueous alkali solution, and recovering an oily condensate of said ether and aniline from the mixture. 0

2. A condensation product of an amine with a terpene halo-alkyl ether, said ether being one in which a terpene carbon atom of the terpene radical is directly bonded to the ether'oxygen atom and in which the halo-alkyl radical contains at least two carbon atoms and bears a halogen substituent on a carbon atom at least one carbon atom removed from the ether oxygen atom.

contains at least two carbon atoms and bears a halogen substituent on a carbon atom at least one carbon atom removed from the ether oxygen atom. V

4. A condensation product of a secondary amine with a terpene halo-alkylether, said ether being one in which a terpene carbon atom of the terpene radical is directly bonded to the ether oxygen atom and in which the halo-alkyl radical contains at least two carbon atoms and bears a: halogen substituent on a carbon atom at least one carbon atom removed from the ether oxygen atom.

5. A condensation product of a tertiary amine with a terpene halo-alkyl ether, said ether being one in which a terpene carbon atom of the terpene radical is directly bonded to the ether oxygen atom and in which the halo-alkyl radical contains at least two carbon atoms and bears a halogen substituent on a carbon atom at least one carbon atom removed from the ether oxygen atom.

6. A condensation product of a primary aromatic amine with a terpene halo-alkyl ether, said ether being one in which a terpene carbon atom of the terpene radical is directly bonded to the ether oxygen atom and in which the halo-alkyl radical contains at least two carbon atoms and bears a halogen substituent on a carbon atom at least one carbon atom removed from the ether oxygen atom.

7. A condensation product of aniline with a terpene halo-alkyl ether, said ether being one in which a terpene carbon atom of the terpene radical is directly bonded to the ether oxygen atom and in which the halo-alkyl radical contains at least two carbon atoms and bears a halogen substituent on a carbon atom .at least one carbon atom removed from the ether oxygen atom.

8. A condensation product of an amine with a terpene chloroalkyl ether, said ether being one in which a terpene carbon atom oi. the terpene radical is directly bonded to the ether oxygen atom and in which the chloroalkyl radical contains at least two carbon atoms and bears a chlorine substituent on a. carbon atom at least one carbon atom removed from the ether oiwgen atom.

9. A condensation product of an amine with a terpene beta-chloroethyl ether, said ether being one in which a terpene carbon atom 01' the terpene radical is directly bonded to the ether oxygen atom.

10. A condensation product of an amine with terpinyl beta-chloroethyl ether.

11. A condensation product of a primary amine with terpinyl beta-chloroethyl ether.

12. A condensation product of a secondary amine with terpinyl beta-chloroethyl ether.

13. A condensation product of a tertiary amine with terpinyl beta-chloroethyl ether.

l4. A condensation product of a primary aromatic amine with terpinyl beta-chloroethyl ether.

15. A condensation product of aniline with terpinyl beta-chloroethyl ether.

16. A condensation product of an alkylolamine with terpinyl beta-chloroethyl ether.

17. A condensation product of a tertiary aliphatic amine with terpinyl beta-chior'oethyl ether.

18. A condensation product of an alkylenediamine with terpinyl beta-chioroethyl ether.

19. The process which comprises condensing an amine with a terpene halo-alkyl ether, said ether being one in which a terpene carbon atom of the terpene radical is directly bonded to the bears a. halogen substituent on a carbon atom 20. The process which comprises condensing an amine with a terpene beta-chloroethyi ether, said ether being one in which a terpene carbon atom oi the terpene radical is directly bonded at least one carbon atom removed Immthe ether 5 to the ether oxygen atom.

oxygen atom.

, mm W. norammnnam. 

